Fruity musk compositions

ABSTRACT

Novel ester compounds and the use of these esters as a fragrance chemicals, suitable for use in creating fragrance, and scents in items such as perfumes, colognes and personal care products are disclosed.

FIELD OF THE INVENTION

[0001] This invention demonstrates that certain keto esters, carbonates,and diesters of alcohols, which comprise newly discovered chemicals, areuseful as fragrance chemicals, which add value when used in finefragrances, cosmetics, toiletries, and related applications.

BACKGROUND OF THE INVENTION

[0002] There is an ongoing need in the fragrance industry to provide newchemicals to give perfumers and other persons ability to create newfragrances for perfumes, colognes and personal care products.

[0003] The use of alcohols and esters in perfume materials is disclosed.See for example, U.S. Pat. Nos. 3,487,102, 6,384,242, and 6,384,269,which disclose alkonates, geranic acid derivatives and estersrespectively, that are suitable as fragrance materials.

[0004] Despite these disclosures and availability of commercial productsthere is an ongoing need for the development of new fragrance chemicalsthat can be used to provide pleasant fragrance to various products.

SUMMARY OF THE INVENTION

[0005] The present invention is directed to the following novelcompounds and use of these novel compounds as fragrance chemicals toenhance fragrance in perfumes, toilet waters, colognes, personalproducts and the like. More specifically, the present invention is amethod for enhancing a perfume by incorporating an olfactory acceptableamount of compounds of the Formula I, II and III shown below:

[0006] where R is selected from methyl [CH3]; ethyl [C₂H₅] and isopropyl[C₃H_(7].)

[0007] As those with skill in the art will appreciate, the abovestructures contain chiral centers. The positions designated with a * mayhave the absolute configuration of “R”, “S” or racemic. The presentinvention includes these racemic mixtures as well as the entantiomersdescribed herein which are suitable as fragrance materials. These andother embodiments of the present invention will be apparent by readingthe following specification.

DETAILED DESCRIPTION OF THE INVENTION

[0008] The present invention discloses the composition of new chemicalentities, not previously disclosed. Furthermore, the present inventionis directed to the use of the compounds, set forth above, in variousfragrance applications.

[0009] We have discovered that these compounds have a fruity, musky odoror note, that is well suited for use as a fragrance chemical, and impartfresh, vibrant, and long-lasting characteristics to perfume andfragrance formulations.

[0010] Using formulae set forth above, the described compounds are thefollowing: Formula R Compound I methyl 1-(3,3-dimethylcyclohexyl) methylmalonate I ethyl 1-(3,3-dimethylcyclohexyl) ethyl malonate I propyl1-(3,3-dimethylcyclohexyl) propyl malonate I isopropyl1-(3,3-dimethylcyclohexyl) isopropyl malonate II methyl1-(3,3-dimethylcyclohexyl) methyl oxalate II ethyl1-(3,3-dimethylcyclohexyl) ethyl oxalate II propyl1-(3,3-dimethylcyclohexyl) propyl oxalate II isopropryl1-(3,3-dimethylcyclohexyl) isopropyl oxalate III methyl1-(3,3-dimethylcyclohexyl) methyl carbonate III ethyl1-(3,3-dimethylcyclohexyl) ethyl carbonate III propyl1-(3,3-dimethylcyclohexyl) propyl carbonate III isopropyl1-(3,3-dimethylcyclohexyl) isopropyl carbonate

[0011] The use of these compounds are widely applicable in currentperfumery products, including the preparation of perfumes and colognes,the perfuming of personal care products such as soaps, shower gels, andhair care products, as well as air fresheners, candles and cosmeticproducts. The compounds can also be used to perfume cleaning agents,such as, but not limited to soaps, detergents, dishwashing materials,scrubbing compositions, window cleaners, and the like.

[0012] In these preparations, the compound of the present invention canbe used alone or in combination with other fragrance compositions,solvents, adjuvants and the like. Those with skill in the art willappreciate the nature and variety of the other ingredients that can beused in combination with the compound of the present invention.

[0013] Many types of fragrances can be employed in the presentinvention, the only limitation being the compatibility with the othercomponents being employed. Suitable fragrances include, but are notlimited to fruit essences such as almond, apple, cherry, grape, pear,pineapple, orange, strawberry, raspberry; musk; and flower scents suchas lavender, rose, iris, and carnation. Other pleasant scents includeherbal and woodland scents derived from pine, spruce and other forestsmells. Fragrances may also be derived from various oils, such asessential oils, or from plant materials such as peppermint, spearmintand the like.

[0014] A list of suitable fragrances is provided in U.S. Pat. No.4,534,891, the contents of which are incorporated by reference as if setforth in its entirety. Another source of suitable fragrances is found inPerfumes, Cosmetics and Soaps, Second Edition, edited by W. A. Poucher,1959. Among the fragrances provided in this treatise are acacia, cassie,chypre, cyclamen, fern, gardenia, hawthorn, heliotrope, honeysuckle,hyacinth, jasmine, lilac, lily, magnolia, mimosa, narcissus, freshly-cuthay, orange blossom, orchid, reseda, sweet pea, trefle, tuberose,vanilla, violet, wallflower, and the like.

[0015] As used herein olfactory effective amount is understood to meanthe amount of compound in perfume compositions the individual componentwill contribute to its particular olfactory characteristics, but theolfactory effect of the perfume composition will be the sum of theeffects of each of the perfume or fragrance ingredients. Thus thecompounds of the invention can be used to alter the aromacharacteristics of the perfume composition by modifying the olfactoryreaction contributed by another ingredient in the composition. Theamount will vary depending on many factors including other ingredients,their relative amounts and the effect that is desired.

[0016] The level of compound of the invention employed in the perfumedarticle varies from about 0.05 to about 40 weight percent, preferablyfrom about 0.1 to about 10 and most preferably from about 1 to about 5weight percent. In addition to the compounds, other agents can be usedin conjunction with the fragrance. Well known materials such assurfactants, emulsifiers, and polymers to encapsulate the fragrance canalso be employed without departing from the scope of the presentinvention.

[0017] Another method of reporting the level of the compound of theinvention in the perfumed composition, i.e., the compounds as a weightpercentage of the materials added to impart the desired fragrance. Thecompounds of the invention can range widely from 0.005 to about 10weight percent of the perfumed composition, and preferably from about0.1 to about 5 weight percent. Those with skill in the art will be ableto employ the desired level of the compound of the invention to providethe desired fragrance and intensity.

[0018] The compounds are prepared by standard traditional esterificationmethods. The starting materials for these compounds is the readilyavailable alcohol alpha,3,3-trimethylcyclohexylmethanol, as disclosed inU.S. Pat. No. 3,487,102, the contents of which are incorporated byreference. This alcohol is then reacted with the corresponding malonate,oxalate or carbonate esters to provide the compounds of the invention,using standard esterification catalysts and reagents.

[0019] The various enantiomers of the invention may be provided bymethods known in the art. One method for producing the enantiomers isstereoselective enzymatic hydrolysis of the racemic ester groups. Asthose with skill in the art appreciate, an enzyme is selected whichselectively hydrolyzed only one enantiomeric ester to the correspondingalcohol, one enantiomer, thereby providing only the other antipodalester.

[0020] Another and preferred method for providing a desired enantiomerof the invention is to employ a chiral alcohol as a starting materialand the corresponding acid to form a series of entantiomerically pureesters.

[0021] The following are provided as specific embodiments of the presentinvention. Other modifications of this invention will be readilyapparent to those skilled in the art, without departing from the scopeof this invention. As used herein, all percentages are weight percent.IFF as used in the examples is understood to mean International Flavors& Fragrances Inc., DPG is understood to mean dipropylene glycol, DEP isunderstood to mean diethyl phthalate. All of the fragrance chemicalsused in the examples can be purchased from IFF, N.Y., N.Y., unlessotherwise noted.

EXAMPLE 1 Preparation of Ethyl 1-(3,3-dimethylcyclohexyl) Ethyl Malonate

[0022] A solution of 2000 grams of diethyl malonate and 500 grams ofalpha, 3,3-trimethylcyclohexanemethanol was heated to 160° C., whiledistilling off ethanol. Vacuum distillation provided 809 grams ofproduct.

[0023] The product had a fruity odor, with apple, pear and musky notespredominating. The odor was long-lasting, survivng 3 days on a smellingblotter.

[0024] The boiling point of the product was 138° C. at 3.5 millimetersof mercury.

[0025] The NMR analysis of the product is the following:

[0026] 0.81-1.66 ppm (m, 9H); 0.88 ppm (s, 3H); 0.91 ppm (s, 3H); 1.19ppm (d, 3H, J=6.4 Hz); 1.29 ppm (t, 3H, J=7.1 Hz); 3.35 ppm (s, 4H);4.21 ppm (q, 2H); 4.75 ppm (m, 1H).

EXAMPLE 2 Preparation of Methyl 1-(3,3-dimethylcyclohexyl) MethylOxalate

[0027] A solution of 2000 grams of dimethyl oxalate and 500 grams ofalpha, 3,3-trimethylcyclohexanemethanol was heated to 165° C., whiledistilling off methanol. Vacuum distillation provided 633 grams ofproduct. The product had a boiling point of 141° C. at 65 millimeters ofmercury.

[0028] The product had a weak musk note, lasting 24 hours on a smellingblotter.

[0029] The NMR analysis of the product is the following.

[0030] 0.82-1.88 ppm (m, 9H); 0.87 ppm (s, 3H); 0.90 ppm (s, 3H); 1.26ppm (d, 3H, J=6.4 Hz); 3.88 ppm (s, 4H); 4.85 ppm (m, 1H).

EXAMPLE 3 Preparation of Ethyl 1-(3,3-dimethylcyclohexyl) Methyl Oxalate

[0031] 50.2 grams (0.36 moles) of ethyl chlorooxalate was added dropwiseto a stirred solution of 46.8 grams (0.3) moles ofalpha-3,3-trimethylcyclohexanemethanol and 35.6 grams (0.45 moles) ofpyridine at 25-30° C. The solution was stirred for one hour at ambienttemperature. The reaction mixture was diluted with 100 milliliters ofheptane, extracted with 100 milliliters of 5 weight percent HCl, andwashed successively with water and 15 weight percent sodium carbonate.Distillation provided 57.3 grams of product.

[0032] The boiling point of product was 98° C. at 0.5 millimeters ofmercury. The product had a musky, woody note, lasting 10 hours on asmelling blotter.

[0033] The NMR analysis of the product was the following:

[0034] 0.71-2.14 ppm (m, 9H); 0.88 ppm (s, 3H); 0.92 ppm (s, 3H); 1.28ppm (d, 3H, J=6.4 Hz); 1.38 ppm (t, 3H, J=6.3 Hz); 4.34 ppm (m, 2H,);4.86 ppm (m, 1H).

EXAMPLE 4 Preparation of Isopropyl 1-(3,3-dimethylcyclohexyl) IsopropylMalonate

[0035] A solution of 500 grams of alpha,3,3-trimethylcyclohexanemethanoland 100 grams of diisopropylmalonate was heated to 165° C. Vacuumdistillation provided 474 grams of product. The product had a boilingpoint of 140° C. at 3.5 mm of mercury. The product had a weak musk note.

[0036] The NMR analysis of the product was the following:

[0037] 0.81-1.68 ppm (m, 9H); 0.88 ppm (s, 3H); 1.19 ppm (d, 3H, J=6.4Hz); 1.27 ppm (d, 6H, J=6.3 Hz); 3.32 ppm (s, 2H,); 4.75 ppm (m, 1H);5.06 ppm (septtet, 1H, J=6.2 Hz).

EXAMPLE 5 Preparation of Ethyl 1-(3,3-dimethylcyclohexyl) EthylCarbonate

[0038] A solution of 500 grams ofalpha,3,3-trimethylcyclohexanemethanol, 100 grams of 20 weight percentsodium ethylate solution and 590 grams of diethylcarbonate was heated atreflux for 12 hours. The reaction mass was cooled and diluted with 1liter of 5 weight percent formic acid. The layers were split. Excessdiethyl carbonate was removed under reduced pressure. Vacuumdistillation provided 180 grams of product having a boiling point of107° C. at 5 millimeters of mercury. The product had a bright fruityberry note, with woody, rose undertones.

[0039] The NMR analysis of the product was the following.

[0040] 0.82-1.85 ppm (m, 9H); 0.88 ppm (s, 3H); 0.91 ppm (s, 3H); 1.23ppm (d, 3H, J=6.4 Hz); 1.31 ppm (t, 3H, J=7.1 Hz); 4.18 ppm (q, 2H,J=7.1 Hz); 4.54 ppm (pentet, 1H, J=6.2 Hz).

EXAMPLE 6 Use of the Fragrance Compounds Prepared in a FragranceComposition

[0041] The fragrance compounds prepared in Examples 1, 3 and 4 above,were used together in the following formulation to provide a fragrancewith citrus notes. Ingredients Parts by Weight Material from Example 450.00 Ethyl Vanillin 10% DPG 5.00 Material from Example 1 40.00 Materialfrom Example 3 128.00 HEDIONE (Firmenich) 10.00 Vanillin 10% PG 10.00Ambrette Seed Oil 0.30 Bergamot Oil 40.00 Patchouli Oil Light 10% DPG5.00 Dipropylene Glycol 131.70

EXAMPLE 7 Fragrance Formulations

[0042] Three different citrus fragrances were prepared using thefragrance compounds prepared in Examples 1, 2 and 3 described above.Version E Version F Version G Parts by Parts by Parts by IngredientsWeight Weight Weight Ethyl Vanillin 10% DPG 5.00 5.00 5.00 Material fromExample 1 — — 218.00 HEDIONE (Firmenich) 10.00 10.00 10.00 Vanillin 10%PG 10.00 10.00 10.00 Ambrette Seed Oil 0.30 0.30 0.30 Bergamot Oil 40.0040.00 40.00 Patchouli Oil Light 10% DPG 5.00 5.00 5.00 DipropyleneGlycol 131.70 131.70 131.70 Material from Example 2 — 218.00 — Materialfrom Example 3 218.00 — —

[0043] The mixtures were found to provide pleasant fragrances withcitrus notes.

EXAMPLE 8 Fragrance Formulations

[0044] Three different citrus/musk versions were prepared using thefragrance materials prepared in Examples 3, 4 and 5 described above.Version E Version F Version G Parts by Parts by Parts by IngredientsWeight Weight Weight Material from Example 3 218.00 — — Ethyl Vanillin10% DPG 5.00 5.00 5.00 Material from Example 4 — 218.00 — Material fromExample 5 — — 218.00 HEDIONE (Firmenich) 10.00 10.00 10.00 Vanillin 10%PG 10.00 10.00 10.00 Ambrette Seed Oil 0.30 0.30 0.30 Bergamot Oil 40.0040.00 40.00 Patchouli Oil Light 5.00 5.00 5.00 10% DPG DipropyleneGlycol 131.70 131.70 131.70

[0045] The above fragrances were found to provide pleasing acceptablefragrances with musky notes and citrus characteristics.

EXAMPLE 9 Use of the Compound of the Present Invention

[0046] Two fragrance formulations were prepared with similarformulations, except that a compound of the present invention isemployed and a homolog compound is employed in the second formulation.The oriental-type fragrance, the formulations are set forth below:Formulation H Formulation I Ingredients Parts by Weight Parts by WeightEthyl Vanillin 10% DPG 5.00 5.00 Material from Example 1 218.00 NoneFret 02-050 Butanedioc acid, 1-(3,3- None 218.00dimethylcyclohexyl)-ethyl ethyl ester Strawberry Musk compound(Firmenich) IFF fret 02-0138 KHARISMAL 10.00 10.00 Vanillin ex Lignin10% 10.00 10.00 DPG Ambrette Seed Oil 0.30 0.30 Bergamot Essential Oil40.00 40.00 Patchouli Oil 10% DPG 5.00 5.00 DPG 131.70 131.70 AMBERIFFcrystals 1% 10.00 10.00 DPG

[0047] The use of the compound from Example 1 Formulation H creates anaura of sensual musk with softer overtones of amber and citrus. The useof the homolog material in Formulation I provides a fragrance that has aweak musk character, with a more citrus character and undertones ofsweet fruit. This example demonstrates that the compounds of the presentinvention are surprisingly a more powerful musk fragrance chemical,having less citrus and sweet fruit notes than structurally similarfragrance materials.

1. A method for improving, enhancing or modifying a fragrance throughthe addition of an olfactory acceptable amount of the compounds selectedfrom the group consisting of:

where R is selected from methyl, ethyl and isopropyl and the carbon atomdesignated with an asterisk * may have the absolute configuration of“R”, “S” or racemic.
 2. The method of claim 1 wherein the fragrance isincorporated into a product selected from perfumes, colognes, candles,toilet waters, cosmetic products, personal care products, fabric careproducts, cleaning products and air fresheners.
 3. The method of claim 2wherein the cleaning product is selected from the group consisting ofsoaps, detergents, dishwashing compositions, scrubbing compounds andwindow cleaners.
 4. The method of claim 2 wherein the product is apersonal care product.
 5. The method of claim 1 wherein the level isfrom about 0.05 to about 40 weight percent.
 6. The method of claim 1wherein the level is from about 0.1 to about 10 weight percent.
 7. Themethod of claim 1 wherein the level is from about 1.0 to about 5 weightpercent.
 8. A compound having the structure selected from the groupconsisting of

where R is selected from methyl, ethyl and isopropyl and the carbon atomdesignated with an asterisk * may have the absolute configuration of“R”, “S” or racemic.
 9. (canceled)
 10. (canceled)
 11. (canceled) 12.(canceled)
 13. The compound of claim 8 which is ethyl1-(3,3-dimethylcyclohexyl) ethyl carbonate.
 14. A fragrance compositioncomprising an olfactory effective amount of the compound of claim 8.